Improving quantification of hydrogen peroxide by synchrotron vacuum ultraviolet photoionization mass spectrometry

Dong, Bin; Hu, Zhihong; Xu, Qiang; Liu, Bingzhi; Zhu, Qingbo; Guan, Jiwen; Liu, Chengyuan; Pan, Yang; Hu, Longhua; Fang, Jun; Wang, Zhandong

doi:10.1016/j.combustflame.2022.112214

Cited by 23 publications

(9 citation statements)

References 24 publications

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“…We have found that if we use the H 2 O 2 cross section reported by Dodson et al, we need to multiply the concentration time profiles from the model by a factor of 2.8 to get good agreement with the experiment. If we use the H 2 O 2 cross section reported by Dong et al which is ∼2.5 times smaller at 11.45 eV, we get good agreement with the experiment and no scaling is necessary. For the data shown in Figure and Table , we use the H 2 O 2 cross section from Dong et al The formaldehyde intensity in the plateau region after 5 ms is very sensitive to the product branching fractions of the CH 3 CO + O 2 reaction.…”

Section: Resultssupporting

confidence: 70%

Conformer-Dependent Chemistry: Experimental Product Branching of the Vinyl Alcohol + OH + O₂ Reaction

et al. 2023

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The concentration of formic acid in Earth’s troposphere is underestimated by detailed chemical models compared to field observations. Phototautomerization of acetaldehyde to its less stable tautomer vinyl alcohol, followed by the OH-initiated oxidation of vinyl alcohol, has been proposed as a missing source of formic acid that improves the agreement between models and field measurements. Theoretical investigations of the OH + vinyl alcohol reaction in excess O2 conclude that OH addition to the α carbon of vinyl alcohol produces formaldehyde + formic acid + OH, whereas OH addition to the β site leads to glycoaldehyde + HO2. Furthermore, these studies predict that the conformeric structure of vinyl alcohol controls the reaction pathway, with the anti-conformer of vinyl alcohol promoting α OH addition, whereas the syn-conformer promotes β addition. However, the two theoretical studies reach different conclusions regarding which set of products dominate. We studied this reaction using time-resolved multiplexed photoionization mass spectrometry to quantify the product branching fractions. Our results, supported by a detailed kinetic model, conclude that the glycoaldehyde product channel (arising mostly from syn-vinyl alcohol) dominates over formic acid production with a 3.6:1.0 branching ratio. This result supports the conclusion of Lei et al. that conformer-dependent hydrogen bonding at the transition state for OH-addition controls the reaction outcome. As a result, tropospheric oxidation of vinyl alcohol creates less formic acid than recently thought, increasing again the discrepancy between models and field observations of Earth’s formic acid budget.

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Section: Resultssupporting

confidence: 70%

Conformer-Dependent Chemistry: Experimental Product Branching of the Vinyl Alcohol + OH + O₂ Reaction

et al. 2023

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“…Additionally, two peroxides (hydrogen peroxide and methyl peroxide), three carboxylic acids (formic acid, acetic acid, and isobutyric acid), and one alcohol (methanol) were detected, identified, and quantified by SVUV-PIMS. The PICSs of formaldehyde, hydrogen peroxide, acetic acid, and methyl peroxide were adopted from the literature studies. − , The PICS of isobutyric acid was measured in this work. Details of the PICS measurement method can be found in previous work, and the table of PICS for isobutyric acid is provided in the Supporting Information.…”

Section: Resultsmentioning

confidence: 99%

“…The PICSs of formaldehyde, hydrogen peroxide, acetic acid, and methyl peroxide were adopted from the literature studies. [25][26][27]42 The PICS of isobutyric acid was measured in this work. Details of the PICS measurement method can be found in previous work, 43 and the table of PICS for isobutyric acid is provided in the Supporting Information.…”

Section: Resultsmentioning

confidence: 99%

Experimental and Updated Kinetic Modeling Study of Neopentane Low Temperature Oxidation

et al. 2023

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Neopentane is an ideal fuel model to study lowtemperature oxidation chemistry. The significant discrepancies between experimental data and simulations using the existing neopentane models indicate that an updated study of neopentane oxidation is needed. In this work, neopentane oxidation experiments are carried out using two jet-stirred reactors (JSRs) at 1 atm, at a residence time of 3 s, and at three different equivalence ratios of 0.5, 0.9, and 1.62. Two different analytical methods (synchrotron vacuum ultraviolet photoionization mass spectrometry and gas chromatography) were used to investigate the species distributions. Numerous oxidation intermediates were detected and quantified, including acetone, 3,3-dimethyloxetane, methacrolein, isobutene, 2-methylpropanal, isobutyric acid, and peroxides, which are valuable for validating the kinetic model describing neopentane oxidation. In the model development, the pressure dependencies of the rate constants for the reaction classes Q ̇OOH + O 2 and Q ̇OOH decompositions are considered. This addition improves the prediction of the low-temperature oxidation reactivity of neopentane. Another focus of model development is to improve the prediction of carboxylic acids formed during the low-temperature oxidation of neopentane. The detection and identification of isobutyric acid indicates the existence of the Korcek mechanism during neopentane oxidation. Regarding the formation of acetic acid, the reaction channels are considered to be initiated from the reactions of O ̇H radical addition to acetaldehyde/acetone. This updated kinetic model is validated extensively against the experimental data in this work and various experimental data available in the literature, including ignition delay times (IDTs) from both shock tubes (STs) and rapid compression machines (RCMs) and JSR speciation data at high temperatures.

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“…The PICSs were measured using the two‐liquid mixing method 41 . The detailed validation of PICSs measured by our instrument has been reported previously 42 . The PICSs of methanol and toluene determined by Zhou et al were used as calibration standards 43 .…”

Section: Methodsmentioning

confidence: 97%

“…41 The detailed validation of PICSs measured by our instrument has been reported previously. 42 The PICSs of methanol and toluene determined by Zhou et al were used as calibration standards. 43 Since the pressure at the sampling position remains constant, the signal change between standard and target molecules under different photon energy is caused by mole fraction, mass discrimination factor and PICS.…”

Section: Measurement Proceduresmentioning

confidence: 99%

Measurement and summary of photoionization data for biomass‐derived compounds

Zhuang

Chen

et al. 2022

Rapid Comm Mass Spectrometry

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Rationale Biomass is a potential feedstock for making liquid fuels and valuable chemicals. Quantitative analysis of biomass conversion in real time by photoionization mass spectrometry (PIMS) is an important way to understand the reaction process. However, the lack of photoionization data for biomass‐derived compounds limits the research using PIMS. Methods Measurements of photoionization data were performed with synchrotron vacuum ultraviolet PIMS. Toluene and methanol were used as calibrated references and solvents in this experiment since their photoionization cross‐sections (PICS) are well documented in the literature. Results The ionization energies (IEs) of 23 biomass‐derived compounds were measured. Among them, the PICSs of 14 compounds were calibrated and presented. Besides, the IEs of 95 other biomass‐derived compounds and their typical fragment ions were also summarized. Conclusions A photoionization database related to IEs and PICSs of biomass‐derived compounds (m/z < 200) is established. PICSs of most biomass‐derived compounds have low values at the most frequently used photoionization energy of 10.5 eV. Lignin‐derived compounds have lower IEs than carbohydrate‐derived compounds.

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Improving quantification of hydrogen peroxide by synchrotron vacuum ultraviolet photoionization mass spectrometry

Cited by 23 publications

References 24 publications

Conformer-Dependent Chemistry: Experimental Product Branching of the Vinyl Alcohol + OH + O₂ Reaction

Conformer-Dependent Chemistry: Experimental Product Branching of the Vinyl Alcohol + OH + O₂ Reaction

Experimental and Updated Kinetic Modeling Study of Neopentane Low Temperature Oxidation

Measurement and summary of photoionization data for biomass‐derived compounds

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Improving quantification of hydrogen peroxide by synchrotron vacuum ultraviolet photoionization mass spectrometry

Cited by 23 publications

References 24 publications

Conformer-Dependent Chemistry: Experimental Product Branching of the Vinyl Alcohol + OH + O2 Reaction

Conformer-Dependent Chemistry: Experimental Product Branching of the Vinyl Alcohol + OH + O2 Reaction

Experimental and Updated Kinetic Modeling Study of Neopentane Low Temperature Oxidation

Measurement and summary of photoionization data for biomass‐derived compounds

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Product

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Conformer-Dependent Chemistry: Experimental Product Branching of the Vinyl Alcohol + OH + O₂ Reaction

Conformer-Dependent Chemistry: Experimental Product Branching of the Vinyl Alcohol + OH + O₂ Reaction